(aryloxyaryl) arylphosphorus compounds

ABSTRACT

Cyano (aryloxyaryl) arylphosphines, and cyano(aryloxyaryl) arylphosphine sulfides have been prepared.

United States Patent Johns 1 June 13, 1972 [54] (ARYLOXYARYL) ARYLPHOSPHORUS COMPOUNDS [72] Inventor: Ira B. Johns, Marblehead, Mass.

[73] Assignee: Monsanto Research Corporation, St.

Louis, Mo.

[62] Division of Ser. No. 459,931, May 28, 1965, Pat. No

[52] use ..260/545P 51 no.0. ..c07r9/s0 [58] Field of Search ..260/545 P [56] References Cited OTHER PUBLICATIONS Johns et al., J. Phys. Chem. 70, 924 1966).

Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Robert Gerstl Attorney-R. M. Dickey, L. A. Ferris and M. B. Moshier [5 7] ABSTRACT Cyano (aryloxyaryl) arylphosphines, and cyano(ary|oxyaryl) arylphosphine sulfides have been prepared.

4 Claims, No Drawings (ARYLOXYARYL) ARYLPHOSPHORUS COMPOUNDS This is a division of application, Ser. No. 459,931, filed May 28, 1965, now U.S. Pat. No. 3,576,861.

This invention relates to new compounds, and more particularly, provides new phosphorus compounds.

The presently provided compounds are characterized by the simultaneous presence of an aryl and an aryloxyaryl radical attached to a trior pentavalent phosphorus atom, and include phosphorus cyanides, halides, cyanophosphine sulfides, and phosphinous and phosphinic acids, as illustrated by the following formula P (X) nY ArOAr in which each Ar is an aromatic hydrocarbon radical, free of aliphatic unsaturation, of from six to 12 carbon atoms, Y is a substituent selected from the class consisting of halogen, cyano and hydroxy groups, X is a chalkogen element having an atomic weight below 35 (i.e., selected from the class consisting of O and S), which is S when Y is cyano and when Y is hydroxy, and n is an integer of from 0 to l, which is 0 when Y=halogen. By an aromatic radical is meant a radical including at least one benzene ring, and which may also include aliphatic radicals; such aromatic radicals are designated by the term aryl herein.

The groups of compounds included in the presently claimed class are interrelated as shown in the following synthesis scheme, from which it will be evident that these compound groups are generally intermediates and products involved in the synthesis of (aryloxyaryl)arylcyanophosphines and their chalkogenides. (The acids, which are an exception to this, are direct derivatives of such intermediates.) The stated cyanophosphine compounds are useful in preparation of poly(nitn'lomethylidynes) as described in my concurrently filed copending application, Ser. No. 459,874, filed May 28, 1965, now U.S. Pat. No. 3,410,809.

AroArPmanz Ar(ArOAr)P-Hal 1 Ar(ArOAr)P-I-lal Ar(ArOAr)P(O)H n) Ar(ArOAr)P-Hal Ar(ArOAr)P-CN (III) 359; Ar(ArOAr)P(S)CN (1v) where Ar and X are as defined above, Hal is a halogen atom of atomic weight below 130, and M is a monovalent metal ion such as Ag or Li.

As the foregoing reaction scheme indicates, novel halo- (aryloxyaryl)arylphosphines are provided by this invention, such compounds being prepared, for example, by the reaction )2+( )2 g Ar(ArOAr)P-Hal (I) Exemplary of this group of compounds are, for example, chloro(p-phenoxyphenyl)phenylphosphine, bromo(p-phenoxyphenyl)phenylphosphine, fluoro(m-phenoxyphenyDphenylphosphine, bromo(o-phenoxyphenyl)phenylphosphine, chloro(p-phenoxyphenyDnaphthylphosphine, chloro(p-phenoxyphenyl)-p-biphenylylphosphine, bromo(m-phenoxynaphthyl)phenylphosphine, iodo(p-naphthoxyphenyl)phenylphosphine, chl0ro(4-o-tolyloxyphenyl)phenylphosphine, chloro (4-o-tolyloxybenzyl)phenylphosphine, chloro(p-phenoxyphenyl)benzylphosphine, bromo(p-phenoxyphenyl)-(tbutylphenyhphosphine, chloro(p-phenoxyphenyl)phenethylphosphine, iodo(p-phenoxy-o-methylphenyl)phenylphosphine and so forth.

The groups of phosphine halides provided as described hereinabove are useful starting materials for the preparation of, alternatively, cyanophosphines and phosphinous acids.

The novel (aryloxyaryl)aryl cyanophosphines provided by this invention, prepared, for example, by the reaction Ar(ArOAr)P-Hal+ MCN Ar(ArOAr)P-CN (111) are exemplified, for example, by cyano(p-phenoxyphenyl) phenylphosphine, cyano(m-phenoxyphenyl)phenylphosphine, cyano(o-phenoxyphenyl)phenylphosphine, cyano(pphenoxyphenyl)phenylphosphine, cyano(p-pheno phenyl) naphthylphosphine, cyano(p-phenoxyphenyl)-p biphenylyllphosphine, cyano(m-phenoxynaphthayl)phenylphosphine, cyano(p-phenoxynaphthyl)benzylphosphine, cyano(p-2,4- xylyloxyphenyl)phenylphosphine, cyano(p-benzyloxyphenyl)biphenylylphosphine, cyano(p-phenoxyphenyl)(iso- ,propyophenyl)phosphine, cyano(p-phenoxy-o-ethylphenyl) phenylphosphine, cyano(p-[pentamethylphenoxy]phenyl) biphenylphosphine and so forth.

The group of presently provided cyanophosphine sulfides ,can be prepared from a cyanophosphine, of the nature stated immediately hereinabove. This reaction is illustrated, for example, by the equation POH (II) and ArOAr P (O) OH (V) .ArO Ar and are derived from the novel aryl(aryloxyaryl)haloph0sphines of this invention by hydrolysis and oxidation.

The hydrolysis of the aryl(aryloxyaryl)halophosphines to produce phosphinous acids is illustrated by the equation:

Ar(ArOAr)P-Hal+ H O Ar(ArOAr)POH (ll) The oxidation of such phosphinous acids is effected, for example, as illustrated by the following equation:

Ar(ArOAr)POH+[O] Ar(ArOAr)P(O)O1-l (V) The overall reaction, if desired, can conveniently be accomplished without isolation of the phosphinous acid, by con ducting the hydrolysis in the presence of an oxidizing agent such as air.

Exemplary of the presently provided phosphinous and phosphinic acids are (p-phenoxyphenyl)phenylphosphinic acid, (p-phenoxyphenyDphenylphosphinous acid, (m-phenoxyphenyDphenylphosphinic acid, (o -phenoxyphenyl)phenylphosphinous acid, acid, (p-phenoxyphenyl)-p-biphenylylphosphinic acid, (mphenoiq naphthyhphenylphosphinous acid, (p-naphthoxynaphthyl)phenylphosphinic acid, (4-o-tolyloxyphenyl) phenylphosphinous acid, (p-phenoxybenzyllphenylphoscyano(p-[o,p-dimethylphenoxyl (p-phenoxyphenyl)napthylphospliinic phinic acid, (p-phenoxyphenyl)benzylphosphinous acid, (pphenoxyphenyl)(t-butylphenyl)phosphinic acid, (p-phenoxyphenyl)(3-phenylpropyl)phosphinic acid, (p-phenoxy-omethylphenyl)phenylphosphinous acid, (p-phenoxymethylphenyl)(2,4-diisopropylphenyl)phosphinic acid and sgforlh dihalide is reacted with a diaryl mercury compound. Exemplary of these are, for example, diphenylmercury, dibiphenylylmercury, dinaphthylmercury, dibenzylmercury, bis(t-butylphenyl)mercury, diphenethylmercury, and so In conducting this reaction, the reactants will be generally contacted in proportions such that the phosphorus compound is present in excess, compared to the mercury compound, to avoid the possibility of displacing both halogen atoms from the phosphorus compound. However, it has been found that as much as two thirds of a mole of the mercury compound per mole of the dichlorophosphine compound can be present in the reaction mixture without excessive production of undesired products such as a triorganophosphine, and with suitable procedures, it may be possible to use even higher ratios, such as equimolar ratios. The reaction is carried out under anhydrous conditions. Presence of an inert reaction medium such as an organic solvent or diluent is not essential, although such a liquid reaction medium may be employed if desired, such as benzene, toluene, diethylbenzene, and the like. Generally, for reasonably short reaction times, the reaction mixture will be heated. Suitable temperatures are generally above 100 C. and may range considerably higher, ,up to 250 C., for example. Temperatures of about 200- 250 C. are usually suitable. 7 W V The above described procedure provides the starting material from which further of the novel compounds of this oxyaryD-arylphosphine, the halo(aryloxyaryl)arylphosphine is reacted with a metal cyanide. Useful cyanides include, for example, metal cyanides such as silver cyanide, lithium cyanide, potassium cyanide, and so forth. Silver cyanide is advantageous because of the insolubility of the silver chloride produced by the reaction. e V V V In conducting the reaction of the halo(arylloxyaryl)- arylphosphine with a metal cyanide, either component may be present in excess, ranging up to as much as moles per 519g of the other reactarg b lt it is usually convenient and suitable to use approximately equimolar quantities of the two reactants Presen 9f n. i l?" ,Q S HlQ Q LWQ d u during the reaction is usually advantageous. Exemplary of such solvents are, for example, benzene, toluene, hexane, ethylene dichloride, the dimethyl ether of diethylene glycol, cyclohexane, and so forth. The temperatures of the reaction may vary from down to about 0 C. up to elevated temperatures as high as say 200 or 250C, but it is usually possible to conduct the reaction with sufficient efficiency and rapidity at moderate temperatures, in the range of 50l50 C.

The reaction of phosphorus thiochloride with a cyano (aryloxyaryl)arylphosphine provides the corresponding cyanophosphine sulfide. In carrying out this reaction, the organophosphorus compound is contacted with the phosphorus thiochloride, while phosphorus trichloride is evolved from the reaction mixture. Usually equimolar quantities of invention may be produced. To provide a cyano(arylthe respective reactants are suitably employed althoigh if 7 per mole of the other, may be used. It is ordinarily advantageous to heat the reaction mixture to above room temperature, although the reaction temperature may vary widely, from down to 0 C. up to temperatures as high as above 250 C., if desired. In general the range of l25l75 C. is usually suitable, where the reaction is conducted under atmospheric pressure.

For conversion of the presently provided halo(aryloxyaryl) arylphosphines to the corresponding phosphinous and phosphinic acids, the phosphorus compound is hydrolyzed and oxidized. Contact with a large excess of water is generally suitable, without more, to produce the hydrolysis. The boiling temperature is usually suitable; the reaction will proceed, though more slowly, at lower temperatures such as room temperature or below, and if desired, can be accelerated by conducting the reaction under pressure, to increase the boiling point of the aqueous reaction medium.

If care is taken to exclude oxidizing agents, the phosphinous acid can be isolated as the product of the hydrolysis. This is an oxygen-sensitive compound which is readily oxidizable to the corresponding phosphinic acid. To produce such oxidation, any of a variety of usual oxidizing agents may be used, such as oxygen, hydrogen peroxide, potassium permanganate, and so forth; oxygen such as oxygen of the air, dissolved in water, is convenient and will usually be preferred. To effect such oxidation, the phosphinous acid can for example be boiled with a large excess of water in a vessel open to the air; air can be bubbled through an aqueous solution or suspension of the acid; the acid can be mixed with aqueous hydrogen peroxide, and so forth. The temperature of the reaction will depend on the oxidizing power of the oxidizing agent selected; it may desirably be as low as 0 C. when a more powerful reagent such as H 0 is employed, particularly when this is more concentrated than, say, 3 percent, and it may desirably be as high as about C. when boiling in water open to the air is used to affect the oxidation.

ln each of the above-discussed reactions, the pressure may range from subatmospheric pressures as low as 0.05 mm Hg up to superatmospheric pressures as high as 5,000 psig, if desired, but usually ambient pressures are suitable. Also, in each case, the reaction product is isolated by usual means, sl: h as distillation, extraction, filtration, and so forth.

The presently provided novel (aryloxyaryl)arylphosphine compounds are generally stable materials, which range from oils to solid crystalline materials, and are useful for a wide variety of agricultural and industrial purposes. For example, the halides and cyanides provided hereby are intermediates for the production of the presently provided cyano(aryloxyaryl)arylphosphine sulfides, which can be converted to polymers as noted hereinabove, by high pressure condensation as described in my concurrently filed copending application Ser. No. 459,814, now U.S. Pat. No. 3,410,809. The stated poly(nitrilomethylidynes) may be employed, for example, as functional fluids, for lubi ication tranfer of heat or other high temperature functional fluid applications. The present compounds may also be employed if desired as agricultural toxicants, to produce kill of vegetation, insects, microbiological organisms such as bacteria and fungi, insects such as the house fly, army worm larvae (Prodenia eridania) and the like.

'l h e in vention i s ihustrated but not limited by the following examples.

EXAMPLE 1 This example describes the preparation of a halo(aryloxyaryl)arylphosphine.

A mixture of 100 grams (g) (0.37 mole) of dichloro-pphenoxyphenylphosphine and 50 g of diphenylmercury (0. [4 mole) is heated, under nitrogen, for four hours at 2 l02 l 5 C The reaction mixture is cooled, triturated with several milliliter (ml) portions of warm ligroin, and the resulting mixture is filtered. The filtrate is distilled to recover 26.0 g of chloro(p-phenyloxyphenyl)phenylphosphine, 162- BCJQQ? E; aa fl-fiflZli f l-. -.D L analysis corresponds to the assigned structure of C H ClOP.

EXAMPLEZ This example describes another preparation of a halo- (aryloxyaryl)arylphosphine.

The procedure of Example 1 is repeated, except that the amount of the diphenylmercury component is increased to 81 g (0.23 mole), and the reaction mixture is heated for two hours, with very rapid mechanical stining. Extraction with petroleum ether and then benzene yields chloro(p-phenoxy- EXAMPLE 3 EXAMPLE4 This example illustrates the preparation of a cyano aryloxyaryl)arylphosphine chalkogenide.

A mixture of 26 g (0.14 mole) of phosphorus thiochloride is heated with 43 g (0.14 mole) of cyano(p-phenoxyphenyl) phenylphosphine at 140 C. bath temperature, until the distillation of phosphorus trichloride has ceased. Distillation of the residual liquid at 174-176 C./0.02 mm provides cyano(p-phenoxyphenyDphenylphosphine sulfide as a heavy ycflm oil, n 1.6576, having an elemental analysis corresponding to the assigned structure of C H NOPS.

A lead capsule enclosing 6.7 g of the cyano (p-phenoxyphenyhphenylphosphine sulfide is placed in a steel pressure of benzene gives a value of immrm mstoa degree of polymerization of approximately 5. The polynitrilomethylidyne product may be employed, for example, as a functional fluid, in areas such as high temperature lubrication or the like.

EXAMPLE 5 wuitu a qiltustra qs he 1591 5221 of an t!- oxyaryl(arylphosphinic acid invention.

A mixture of 2 grams of chloro(p-phenoxyphenyl)phenylphosphine with excess water is boiled for several hours and then let stand overnight. The cooled reaction mixture contains a powdery white solid which is filtered off, dried, and recrystallized from benzene and petroleum ether. The P QPSL .(BLPBEPLXPI'EBYQPEQPHPJEPHlQL3 b. m 157158 C., having an elemental analysis corresponding to the assigned structure C18H1503P.

While the invention has been described with particular reference to specific preferred embodiments thereof, it will be appreciated that modifications and variations can be made without departing from the scope of the invention, as disclosed herein, which is limited only as described in the appended claims.

What is claimed is:

1. A cyano(ary1oxyaryl)arylphosphine of the formula Ar(ArOAr)P-CN, in which each Ar is an aromatic hydrocarbon radical free of aliphatic unsaturation and containing from six to 12 carbon atoms.

2. Cyano(p-phenoxyphenyl)phenyl phosphine.

3. Cyano(aryloxyaryl)arylphosphine sulfides of the formula Ar(ArOAr)P(S)CN in which each Ar is an aromatic hydrocarbon radical free of aliphatic unsaturation of from six 0 a bqnatomstw. v .2 WW W.

4. Cyano(p-phenoxyphenyhphenylphosphine sulfide.

i i i i in accordance with this 

2. Cyano(p-phenoxyphenyl)phenyl phosphine.
 3. Cyano(aryloxyaryl)arylphosphine sulfides of the formula Ar(ArOAr)P(S)CN in which each Ar is an aromatic hydrocarbon radical free of aliphatic unsaturation of from six to 12 carbon atoms.
 4. Cyano(p-phenoxyphenyl)phenylphosphine sulfide. 